All United States patents referred to herein are hereby incorporated by reference in their entireties. In the case of conflict, the present specification, including definitions, will control.
Solar control coatings on transparent panels or substrates are designed to permit the passage of visible light while blocking infrared (IR) radiation. High visible transmittance, low emissivity coatings on, e.g., architectural glass and automobile windows can lead to substantial savings in costs associated with environmental control, such as heating and cooling costs.
Generally speaking, coatings that provide for high visible transmittance and low emissivity are made up of a stack, which typically includes a transparent substrate and an optical coating. The stack includes one or more thin metallic layers, with high IR reflectance and low transmissivity, disposed between anti-reflective dielectric layers. These systems reflect radiant heat and provide insulation from the cold as well as from solar radiation. Most low-e stacks in use today are based on transparent dielectrics. In general, the thickness of the dielectric layers are tuned in to reduce inside and outside reflectance so that the light transmittance is high (>60%). The IR reflective metallic layers may be virtually any reflective metal, such as silver, copper, or gold. Silver (Ag) is most frequently used for this application due to its relatively neutral color. The anti-reflective dielectric layers are generally transparent material selected to enhance visible transmittance.
Conventional low emissivity coatings generally strive to maintain reflection relatively constant throughout the visible spectrum so that the coating has a “neutral” color; i.e., is essentially colorless. However, conventional low-emissivity coatings fail to provide the extremes of reflected color required for aesthetic and other reasons by certain applications.
To achieve the desired properties in a coated substrate, the composition and thickness of each of the layers of a multilayer coating must be chosen carefully. For example, the thickness of an IR reflective layer such as Ag must be chosen carefully. It is well known that the emissivity of a Ag layer tends to decrease with decreasing Ag sheet resistance. Thus, to obtain a low emissivity Ag layer, the sheet resistance of the Ag layer should be as low as possible. However, increasing Ag layer thickness will also cause visible transmission to decrease and can result in colors that are generally undesirable. It would be desirable to be able to increase visible transmission by decreasing Ag layer thickness without increasing sheet resistance and emissivity.
Thin, transparent metal layers of Ag are susceptible to corrosion when they are brought into contact, under moist or wet conditions, with various corrosive agents, such as atmosphere-carried chlorides, sulfides, sulfur dioxide and the like. To protect the Ag layers, various barrier layers can be deposited on the Ag. However, the protection provided by conventional barrier layers is frequently inadequate.
Coated glass is used in a number of applications where the coating is exposed to elevated temperatures. For example, coatings on glass windows in self-cleaning kitchen ovens are repeatedly raised to cooking temperatures of 120-230° C., with frequent excursions to, e.g., 480° C. during cleaning cycles. In addition, when coated glass is tempered or bent, the coating is heated along with the glass to temperatures on the order of 600° C. and above for periods of time up to several minutes. These thermal treatments can cause the optical properties of Ag coatings to deteriorate irreversibly. This deterioration can result from oxidation of the Ag by oxygen diffusing across layers above and below the Ag. The deterioration can also result from reaction of the Ag with alkaline ions, such as sodium (Na+), migrating from the glass. The diffusion of the oxygen or alkaline ions can be facilitated and amplified by the deterioration or structural modification of the dielectric layers above and below the Ag. Coatings must be able to withstand these elevated temperatures. However, previously known multilayer coatings employing Ag as an infrared reflective film frequently cannot withstand such temperatures without some deterioration of the Ag film.
Low emissivity coatings are described in U.S. Pat. Nos. 4,749,397 and 4,995,895. Vacuum deposited low emissivity coatings containing silver are presently sold in the fenestration marketplace.
U.S. Pat. No. 4,995,895 teaches the use of oxidizable metals as haze reduction topcoats useful for protecting temperable low-e coatings. This patent is directed to methods of reducing haze resulting from exposure to temperatures over 600° C.
Metal, metal alloy and metal oxide coatings have been applied to low emissivity silver coatings to improve the properties of the coated object. U.S. Pat. No. 4,995,895 describes a metal or metal alloy layer which is deposited as the outermost layer of the total layers applied to a glass base. The metal or metal alloy layer is oxidized and acts as an anti-reflection coating. U.S. Pat. No. 4,749,397 describes a method where a metal oxide layer is deposited as an antireflection layer. Sandwiching the silver layer between anti-reflection layers optimizes light transmission.
Unfortunately, optical coatings are frequently damaged during shipping and handling, including by scratching and by exposure to corrosive environments. Silver based low-emissivity coatings are particularly susceptible to corrosion problems. Most low emissivity stacks in use today make use of barrier layers somewhere in or on the low emissivity thin layer stack to reduce these problems. Thin barriers function to reduce the corrosion of silver layers from water vapor, oxygen or other fluids. Some reduce damage from physical scratching of the low emissivity stack by virtue of their hardness or by lowering friction if they form the outer layer.
For sub-desert areas as well as regions with an intense sun load, the current high transmittance low-e products are already bringing advantages, but the heat and light load is still too high to maximize the thermal and visual comfort inside the houses and buildings in which such low-e products are being used.
A few low-e stacks with lower light transmittance are available, but such products usually exhibit at least one of the following draw backs: high reflectance, which makes them less aesthetically appealing, or high shading coefficient, which makes them inappropriate for controlling the heat load.
Very few commercially available low-e products combine the desired optical properties and shading coefficient. Those that do still require additional modifications to make them ideal for processing and production. Further, such low-e coatings are soft coatings that require extra attention during storage and processing into an insulating glass unit. It is desirable to improve the current mechanical and chemical durability of such coatings.
Producing different stack designs on the same coater also can often present a problem because the set-up requirements are not always compatible between the different designs. It would be desirable to provide different coatings that can be produced simultaneously on a coater without requiring down time and modification of the coater layout.
Furthermore, for safety reasons, more glass is now being heat treated to increase its mechanical strength and avoid laceration in case of breakage. This is especially true for low SHGC products. The increase in energy absorption of the coating increases the potential thermal stress on the light when part of it is exposed to the sun radiation and part of it is in the shade. Typical low-e coatings are not designed to withstand thermal strengthening or tempering. Such conditions can completely damage the coating, destroying its aesthetic appeal, thereby rendering it unusable.
PPG has made a low SHGC product available on the market but it is characterized by a very significant high light reflectance (see LBL Window5 database). Moreover, it is Applicant's understanding that this product can be difficult to handle because of a tendency toward scratching. PPG patent application WO 03/020656/A1 describes the making of coatings characterized by a SHGC below 0.38 (i.e., 38%), but having a light reflection exceeding 20%, resulting in a mirror-like look, which is inappropriate for many applications.
Cardinal patent application CA 2 428 860 describes a coating with a low SHGC and appealing aesthetic characteristics. There is no reference to its chemical and mechanical durability, but notably the application does not refer to a double layer of the type NiCrOx/NiCr, which layer is beneficial for the durability of the coating. Furthermore, the use of Zn oxide as primary dielectric material makes it difficult or impossible to temper the coating.
Guardian WO 2003/042122 refers to the sputtering of double Ag temperable products with multiple barriers. However, only coatings with high light transmittance are described.
Guardian WO 02/062717 refers to low light transmittance coatings that are characterized by the ability to be tempered. However, only single Ag coatings with SHGC higher than 0.40 are exemplified.
St. Gobain patent application WO 03/010105 refers to stacks including the following sequence: dielectric/Absorbing layer (metallic, eventually nitrided)/Ag/dielectric. The presence of a metallic layer under the Ag tends to decrease the Ag nucleation. It also weakens the mechanical durability of the stack.
St. Gobain application WO 02/48065 describes the use of absorbing materials in a low-e stack in order to control light transmittance. The application focuses on cladding the absorbing layer between 2 dielectrics. This is intended to improve the thermal stability of the stack during heat treatment. Notwithstanding whether or not the location of the absorbing layer surrounded by dielectric material provides some advantages in insuring thermal stability, this configuration is inconvenient and results in inefficient production. The sputtering of the absorbing layer will be affected by “gas cross talk” inside the coater. This makes the nature of the absorbing layer less controllable and the long term stability questionable. For instance, if a layer of absorbing TiN is sputtered next to an oxide dielectric coat zone, the TiN will be contaminated by oxygen. The TiN layer would then be less absorbing. These problems might be addressed by improving the gas insulation of each coat zone, but this process is costly and undesirable for the production of other low-e coatings on the same coater.
CPFilms U.S. Pat. No. 6,007,901 refers to layer systems based on double metallic barriers.
There thus remains a need for low emissivity coating stacks (and methods of making them) that overcome the various problems seen in the prior art. In particular, there is a need for low-e stacks having a low solar heat gain coefficient, which stacks exhibit retained or increased aesthetic appeal, and mechanical and/or chemical durability, and which can be tempered or heat strengthened, if desired. Moreover, there is a need for stacks that can be applied without need for a specific, nonstandard coater.